High surface area alloys of nickel with molybdenum and tungsten

ABSTRACT

HIGHLY DISPERSED ALLOY MATERIALS OF NICKEL AND MOLYBDENUM AND/OR TUNGSTEN HAVING A VERY HIGH SURFACE AREA ARE MADE BY THE CONTROLLED REDUCTION OF A MXTURE OF COMPOUNDS OF THE METALS IN A REDUCING ATMOSPHERE. THESE ALLOYS AND THEIR SULFIDES ARE USEFUL IN CATALYSIS SUCH AS HYDROCRACKING, HYDROGENATION-DEHYDROGENATION AND HYDROISOMERIZATION.

United States Patent C) US. Cl. 252-439 18 Claims ABSTRACT OF THEDISCLOSURE Highly dispersed alloy materials of nickel and molybdenumand/ or tungsten having a very high surface area are made by thecontrolled reduction of a mixture of compounds of the metals in areducing atmosphere. These alloys and their sulfides are useful incatalysis such as hydrocracking, hydrogenation-dehydrogenation andhydroisomerization.

This invention relates to novel alloys of nickel with molybdenum andtungsten and their sulfides of very high surface areas, to methods ofmaking these materials, and to their use as catalysts.

Nickel and tungsten and nickel and molybdenum form metallurgical alloysby the fusion of a mixture of powders of the two metals. Alloys of thesemetals are also prepared by the cathodic electrodeposition of the metalsfrom solutions containing the metals. However, alloys formed by thesetechniques have essentially no surface area and are not suitable ascatalyst materials.

It is well recognized in the metallurgical arts that a temperaturegreater than 500 C. is required to reduce molybdenum oxide to molybdenummetal with hydrogen and a temperature greater than 650 C. is required toreduce tungsten oxide to tungsten metal with hydrogen. Furthermore, it sknown that nickel tungstate and nickel molybdate are reduced to themetals in hydrogen only at a temperature in excess of 500 C. However, atthese high temperatures the resulting alloys are sintered or fused to aproduct having essentially no surface area. In experimenting with mixedoxides of nickel and tungsten or nickel and molybdenum we found thatsignificant amounts of nickel tungstate or nickel molybdate are formedwhen the oxides are heated at a temperature above about 400 C. Whenthese mixed oxides of nickel and tungsten or nickel and molybdenum areheated in the presence of hydrogen at a temperature such as 400 C., ahighly exothermic reaction takes place resulting in the production ofsome free nickel metal together with nickel tungstate or nickelmolybdate but only a small amount, if any, of alloy is formed.

In the face of this knowledge we have made the surprising discovery thatsubstantial amounts of the alloys of nickel and tungsten or nickel andmolybdenum are produced by subjecting a mixture of reducible compoundsof the metals, preferably the hydrated mixed oxides, to a controlledtemperature treatment in a reducing atmosphere. The resulting product isa fine, highly dipersed powder of high surface area containingsubstantial amounts of an alloy of nickel and tungsten and/or molybdenumwhich can be sulfided to produce mixed metallic sulfides of very highsurface areas. The exceptionally high surface area of these newmaterials is a distinguishing characteristic of substantial significancein their catalytic efiicacy. In some instances the surface area exceeds200 square meters per gram.

These novel alloy materials include nickel-tungsten alloys,nickel-molybdenum alloys and nickel-tungsten- "ice molybdenum alloys. Intheir broadest range these alloy materials will possess from about 5 toabout mol percent nickel, while in their preferred range they will havefrom about 30 to about 85 mol percent nickel. Furthermore, the mol ratioof nickel to the second component, that is molybdenum and/or tungsten,in the alloy material can vary between about 50 to 1 and about 0.2 to 1in the broad range and between about 15 to 1 and about 1 to 1 in thepreferred range. These alloys are formed by the controlled reduction ofreducible compounds such as a mixture of the hydrated oxides of themetals in a reducing atmosphere at relatively mild conditions. Theresulting product is a mixture of the alloy or mixed alloys togetherwith a minor amount of metal oxide or mixed metal oxides. We weresurprised to discover the presence of tungsten and/or molybdenum metalin the final product as the result of the relatively mild reductionconditions employed particularly in view of the rigorous conditionsrequired for the separate reduction of these relatively intractablemetals. We were also surprised to discover that alloy materials ofsignificant surface area were not produced by following the proceduresof our invention when either iron or cobalt was substituted for thenickel.

In accordance with our preferred procedure for pro ducing the alloys,the material undergoing reduction is initially heated at a relativelylow base temperature in a reducing atmosphere and is then heated at ahigher temperature in a reducing atmosphere to complete the treatment.This initial reduction is conducted between about C. and about 250 C.,preferably a maximum of about 200 C. The reduction is then carried outat a temperature above about 250 C. and up to about 600 C. for the finalreduction treatment. The maximum temperature for superior alloyformation and surface area is preferably restricted to a temperature ofabout 450 C. and most preferably a maximum temperature of about 400 C.particularly for those compositions containing tungsten.

Although this reduction procedure is considered to be a two-phaseprocedure in its broadest aspect, that is, the first phase being carriedout at a temperature between about 100 C. and about 250 C. and thesecond phase being carried out at atemperature above about 250 C. and upto about 600 C., the actual operation can be carried out according to avariety of techniques. Thus the reduction treatment can be initiated atan initial temperature within the first phase of operation and raised atan appropriate rate in a series of steps or at a continuous rate to themaximum desired temperature. For example, the hydrogen reduction of themixture of metal compounds can be initiated at 100 C. with thetemperature raised at a rate of 2 C. per minute to a maximum temperatureof 400 C. and then maintained at this final temperature of 400 C. fortwo hours. In another procedure, the reduction is carried out over aseries of suitable finite temperature increments. For example, reductioncan be initiated at 200 C. and at succeeding higher temperature levelssuch as 50 C. or 100 C. higher in each level until the maximum desiredtemperature is reached, provided that reduction at each temperaturelevel is carried out for sufiicient time, such as two hours, toeffectuate satisfactory reduction at each level.

If the initial reduction is initiated at a temperature above about 250C., an uncontrolled highly exothermic reaction takes place resulting inoverheating and consequent calcination and fusing of the material and/ortungstate or molybdate formation without significant alloy formation orsurface area formation and without significant catalytic activity in theresulting material. We believe that the initial reduction in ourpreferred two-phase reduction treatment effects the highly exothermicphase of the reduction at a rate which prevents the aforementionedadverse elfects. It has been determined for superior re sults accordingto this two-phase procedure that the first phase treatment be conductedunder such conditions that a highly exothermic reaction is substantiallyreduced or eliminated in the second phase of the treatment. Therefore,the temperatures and duration of treatment must be properly correlatedin any specific procedure utilized in order to effectuate adequatereduction while avoiding these adverse effects.

As an alternate procedure, the mixed metal feed composition can bereduced at a constant relatively high temperature, for example 400 C.under conditions which control the exothermic reaction. One suchprocedure involves reduction with internal cooling of the materialundergoing reduction. Another procedure involves the use of a hydrogenstream admixed with a significant quantity of an inert diluent gas suchas nitrogen to limit the rate of reduction and carry off heat as it isgenerated. Also combinations of these procedures or equivalentprocedures can be utilized.

The product after completion of the reduction treatment without furtherconditioning is highly pyrophoric upon exposure to air and must eitherbe used in this state under water, hydrocarbon oil or their equivalentin the absence of oxygen or it must be partially deactivated. In thisdeactivation treatment we prefer to pass a stream of nitrogen containinga trace of oxygen, such as ppm, over the reduced product at roomtemperature or lower until the material has been stabilized againstattack by air. Alternatively, a stream of carbon dioxide or other inertgas containing a minute amount of oxygen can also be used fordeactivation. Following this deactivation procedure, exposure of thematerial to air at room temperature is accompanied by a warming of thematerial, indicating a still further mild oxidation of the material.Although this deactivation results in the partial oxidation of thematerial, it permits it to be further handled in atmospheric air and tobe used for catalytic purposes as any conventional catalyst withoutspecial precautions.

The product of the first phase of the two-phase reduction procedure,that is reduction carried out at a temperature no higher than 250 C., isextremely pyrophoric upon exposure to air and therefore analysis of thismaterial is impractical. We have found that this material cannoteffectively be deactivated for use by the above specified procedure. Webelieve that the product of the first phase of this reduction procedureis a very intimate mixture of partially reduced oxides which areextremely reactive to reoxidation and that the second phase is requiredto increase the degree of reduction and place the material in a formwhich has less tendency to reoxidize. Even then, as pointed out, thefinal material must be subjected to a controlled partial reoxidation topermit it to be exposed to air.

We have discovered that the final temperature at which the reductiontreatment is conducted influences the surface area of the final product.That is the higher the final temperature, the lower is the surface areauntil at a temperature at about 600 C. or above the material fuses andcoalesces. However, the lower the final temperature of treatment thelonger the period of treatment that is required. Therefore, the finaltemperature of treatment affects both the required time of treatment andthe surface area of the final product.

We prefer to use the coprecipitated hydrated metal oxides of the desiredmetals as the feed material to our reduction process. Other mixedreducible compounds of the metals such as the oxides, carbonates,acetates, oxalates, etc., are usable herein. It is preferred to usecoprecipitated compounds of the metals in order to obtain a moreintimate mixture, however, a mixture of the compounds which have beenintimately mixed in the solid form, such as by grinding together thesolid compounds of the metals, can also be utilized. In producing thesemetal containing feed mixtures, it is important to avoid the inclusionof any undesired cationic constituent which would remain in the finalproduct after the reduction treatment.

The final product of the reduction treatment and deactivation asdescribed contains a nickel-tungsten and/or molybdenum alloy as a majorcomponent. X-ray diffraction analysis of the preparation indicates thatthe alloy is a solid solution of molybdenum and/or tungsten in nickel inwhich the molybdenum and/or tungsten is incorporated into the basicnickel lattice. However, the term alloy is used herein in its broadgeneral sense, that is, to include intermetallic compounds, solidsolutions of the metals or mixtures thereof in crystalline or amorphousphases, or mixtures thereof.

Elemental analysis of this final product also indicates the presence ofoxygen. The amount of oxygen that is present as the result of incompletereduction of the material has not been determined separately from theamount that is incorporated in the deactivation procedure and uponsubsequent exposure to air. The final product is determined to be one ormore alloy phases in admixture with one or more metal oxide or suboxidephases in crystalline, partially crystalline and/ or amorphous phases.In the high nickel compositions such as those containing about four molsof nickel for each mol of the other metal, X-ray diffraction analysisindicates a strong alloy phase and a minor amorphous phase. As this molratio is re duced to about three, a small tungsten suboxide phaseappears together with a strong alloy phase and a more significantamorphous phase. When the mol ratio is reduced further to about one, thecrystalline tungsten suboxide phase becomes more significant togetherwith a strong alloy phase and an equivalent amorphous phase. When themol ratio is further reduced to about one-third, the tungsten suboxidephase predominates over the alloy phase along with the appearance of atungsten and/or molybdenum metal phase and a reduced amorphous phase.These observations indicate that a mol ratio of nickel to the othermetals of greater than about one is preferred for superior alloyformation. The alloy in our composition is the major constituent andconstitutes greater than percent in the higher ranges of nickel contentwith the oxide phases being only a minor constituent. It has beenobserved, in general that the oxygen content decreases as the nickelcontent of the material increases.

When these materials containing the metal alloys are treated in asulfiding atmosphere, such as one containing hydrogen sulfide, undersulfiding conditions, various sulfides of the metals are produced. Theparticular sulfide of nickel, of which there are several, that isproduced is in part dependent upon the particular temperature used andthe concentration of the hydrogen sulfide in the sulfiding gas. It issignificant that the sulfiding operation produces the metal sulfides asa result of a sulfiding of the metals present as well as a significantsulfiding of the metal oxides and/or suboxides present in the material,therefore the oxygen content of the sulfided material is significantlylower than the oxygen content of the nonsulfided material. Thissulfiding procedure is effected with only a slight reduction of thesurface area of the alloy material, that is, the resulting sulfidedproduct possesses an unusually high surface area. This sulfiding can beconveniently carried out at any suitable temperature such as atemperature between about 250 C. and about 400 C.

In order to point out more fully the nature of the present invention thefollowing specific examples are set forth without any intention oflimiting the invention.

EXAMPLE 1 A solution containing 65.5 grams of nickel nitrate hexahydrateand 6.3 grams of ammonium rnetatungstate, (NH W O -8H O in 375 ml. ofwater was mixed with 500 ml. of 8 molar ammonium hydroxide. Theprecipitate obtained by stirring and heating the mixture until the pHreached between 7 and 8 was filtered by suction and dried at 120 C. forhours. Analysis of this material, preparation 1, together with threeother materials prepared in the same manner but using differentproportions of the nickel and tungsten compounds are set forth in TableI. The water content was determined by thermal gravimetric analysis andthe nonwater oxygen by difference. These materials are called hydratedmetal oxides or metal oxide hydrates, although their precise structureEach of the preparations listed in Table I was separately packed in atube and slowly reduced with hydrogen which was passed over each samplefor two hours at each of the following temperatures in the sequence 250,300, 350 and 400 C. at a gas hourly space velocity of approximately 200hour- At the completion of each reduction cycle the sample tube wascooled to 78 C. and dried nitrogen was passed over the sample for threehours. Each tube was then left open to the atmosphere at C. forapproximately 20 hours. The analysis in weight percent of the componentsof these resulting reduced materials following deactivation and exposureto air as well as surface area in square meters per gram is set forth inTable II.

An X-ray diffraction analysis indicates that a major crystallinecomponent in preparations 1, 2 and 3 and a minor component inpreparation 4 is a solid solution of tungsten in nickel. This solidsolution or alloy retains the basic nickel lattice with an expandedcubic unit cell in accommodation of the larger atomic radius of thetungsten. The unit cell size of this crystalline alloy was determined tobe constant within the limits of error of the measurements even thoughthe over-all nickel-tungsten ratio varied from sample to sample. Apoorly crystallized tungsten suboxide phase appears in a minor amount inpreparation 2, in greater amount in preparation 3, and in major amountin preparation 4. Also observed in the pattern for preparation 1 was apoorly crystallized or amorphous phase which was more predominant inpreparations 2 through 4. A significant amount of nonalloyed tungstenmetal was identified in the pattern of preparation 4. The d spacings andrelative intensities of the X-ray EXAMPLE 3 The procedure of Example 1was followed using varying proportions of nickel nitrate hexahydrate andammonium molybdate. The analysis of the nickel-molybdenum oxide hydratesproduced thereby are set forth in Table III.

TABLE III Ni, Mo, 0, H20. weight weight weight weight percent percentpercent percent Preparation:

EXAMPLE 4 The materials resulting from the procedures of Example 3 werereduced in accordance with the procedures of Example 2. The analysis inweight percent of the reduced material after deactivation and exposureto air is set forth in Table IV.

TABLE IV Ni/Mo,

mol/ N1 M0 0 mol SA Preparation:

The nickel-molybdenum alloy formed in preparations 5, 6 and 7 of TableIV has an X-ray dilfraction pattern very similar to that shown underExample 2 for the nickeltungsten alloy. The principal difierence is thatthe lines of the nickel-molybdenum pattern are broader and moreasymmetrical than those for nickel-tungsten, which suggests that thenickel-molybdenum solid solution obtained is not as homogeneous incomposition or is not as well crystallized as the nickel-tungsten solidsolution or alloy.

Nickel-tungsten-molybdenum alloys are produced using the same proceduresas described in Examples 1 to 4 from the hydrated metal oxide mixtureobtained by precipitation from a solution of suitable compounds of thethree metals.

EXAMPLE 5 Preparation 2 of Table I was reduced at 250 C. for two hoursand at 300 C. for two hours using the same general procedure set forthin Example 2. Without deactivation or exposure to air, the sample wasthen subjected to a stream of hydrogen sulfide in hydrogen in avolumetric ratio of 1 to 4 at 300 C. and a space velocity of about 300vol./vol./hr. for two hours. The resulting product contained nickelsulfide and tungsten sulfide but no combined nickel-tungsten sulfide asdetermined by X-ray diffraction analysis. It analyzed as 31.5 Weightpercent nickel, 35.1 percent tungsten, 27.7 percent sulfur and 5.6percent oxygen and possessed a surface area of 46.4 m. /g. Additionalexperiments showed that the sulfide species and the surface areas areaffected by the temperature of the sulfiding, the concentration of thehydrogen sulfide and the composition of the reduced alloy composition.

EXAMPLE 6 The procedures of Example 5 were followed using preparation 7of Table III. The reduction was at 250 C. for two hours and 300 C. fortwo hours. Sulfiding was carried out at 350 C. for two hours. Theproduct contained a nickel sulfide and molybdenum sulfide but nocombined nickel-molybdenum sulfide. The product analyzed as 27.3 weightpercent nickel, 35.9 percent molybdenum and 36.8 percent sulfur. Thesulfided mixture had a surface area of 35 mF/g.

The various metal alloy and metal sulfide materials, examples of whichare described above, are useful as catalysts in various hydrocarbonreactions including bydrogenation-dehydrogenation such as the gas phasedehydrogenation of cyclohexane, hydrocracking and hydroisomerization.The following examples describe uses of these materials as catalysts.

EXAMPLE 7 n-Octane was hydrocracked in separate runs using preparation lof Table II and preparation 6 of Table IV and compared with nickel metalprepared from dry nickel hydroxide by the procedures set forth inExample 2. These catalysts were pelleted to to mesh size. Hydrocrackingwas carried out at 400 C. and at atmospheric pressure using a liquidhourly space velocity of n-octane of 0.43 hour and a hydrogen ton-octane mol ratio of 1.5.

The nickel converted 68 percent of the n-octane to 100 percent gasproduct, primarily methane, the nickel-tungsten catalyst converted 33percent of the n-octane to 50 percent liquid product, and the nickelmolybdenum converted 45.4 percent of the n-octane to 68 percent liquidproduct. The liquid product in both instances was mainly C and Chydrocarbons with a minor fraction of ethyl benzene. These resultsillustrate the significant difference in catalytic effect between thealloy materials and the nickel metal. These results also furtherindicate that the nickel is combined in the two metal componentcatalysts since gas formation would be the product with free nickel.

EXAMPLE 8 Preparation 3 of Table II and a nickel catalyst prepared asdescribed in the preceding example were compared in thehydroisomerization of l-hexene at a temperature of 350 C. andatmospheric pressure using a liquid hourly space velocity of 1.0 basedon the l-hexene and a hydrogen to l-hexene mol ratio of 7.5. In eachinstance the catalyst was 10 to mesh size. The nickel converted 23percent of the l-hexene with a selectivity of 53 percent to branched Cacyclic compounds, while the nickel-tungsten catalyst converted 50percent of the 1- hexene with a selectivity of 88 percent to branched Cacyclic compounds.

EXAMPLE 9 Preparation 2 of Table II in powder form and a powdered nickelcatalyst prepared as described in Example 7 were compared in the liquidphase hydrogenation of 1- hexene. In each experiment 0.5 gram of thecatalyst was added to a mixture f0 0.1 6 mol of l-hexene, 0.25 mol ofacetic acid and 0.25 mol of methanol in a 100 ml. stainless steelautoclave. Hydrogen was then introduced at 150 p.s.i.g. and thetemperature was raised to 100 C. and held there for three hours. Thenickel-tungsten catalyst hydrogenated 81 percent of the l-hexene whileno hydrogenation occured with the nickel catalyst.

As indicated these novel catalytic materials can be used in a powderedform or in pelleted or extruded form. Additionally they can be mixedwith suitable solid diluents or dispersants. These dispersants canprovide a separate catalytic function in addition to that provided bythe metal alloy when in use or they can be catalytically inert. Examplesof such materials are alumina, silicaalumina, carbon, silicon carbide,granular or powdered polymeric materials such as fiuorinated hydrocarbonpolymer, etc.

These dispersed alloy materials can be produced by directly mixing thepowdered alloy material with the dispersant or by mixing the unreducedmetal ocmpounds, such as the hydrated metal oxides, with the dispersantand then reducing the resulting mixture in the described manner. Thesedispersed mixtures can contain any suitable proportion of alloy materialand dispersant, desirably about 5 to about 50 volume percent of thealloy material and more desirably about 10 to 30 volume percent of thealloy material. The following examples relate to dispersed catalysts.

EXAMPLE 10 45.9 grams of preparation 2 of Table I were mixed with 137.4grams of a commercially available high surface area silica-aluminacontaining 75 percent silica and 25 percent alumina. The mixture wascooked in boiling water for five hours and then dried at 120 F. Themixture was then formed into 10 to 20 mesh pellets and reduced accordingto the procedures of Example 2. Next, grams of the reduced mixture werecharged to a reactor and treated for one hour at 600 F. and at oneatmosphere pressure with a hydrogen-hydrogen sulfide mixture containingeight percent hydrogen sulfide. Following this an FCC furnace oil waspassed over the catalyst at a liquid hourly space velocity of 2.0 and ata temperature of 600 F. and a pressure of 1000 p.s.i.g. together with10,000 s.c.f. of hydrogen per barrel of charge. During an eight hour run19 percent of the furnace oil was cracked.

EXAMPLE 11 Preparation 3 of Table H was dispersed with the silicaaluminaused in the preceding example using the same proportions and procedures.This material was used for the hydroisomerization of l-hexene at thesame conditions used in Example 8, resulting in 83 percent conversionwith an 88 percent selectivity to branched C acyclic compounds.

In another example powdered alloy material, such as preparation 2 ofTable II or preparation 2 of Table IV, is mixed with powdered Teflon(fluorocarbon resin produced by E. I. du Pont de Nemours Company) insuitable proportions such as an equal volume mix. After thorough mixingthe mixture is cast into a sheet and used in fuel cells as a catalyst.

As indicated, the surface area of the resulting alloy materials isaffected by the maximum temperature of the reduction treatment. Thisfeature permits a significant control of the final surface area of thematerial. For catalytic purposes it is desirable to prepare a finalproduct with a surface area of at least one square meter per gram,however, it is preferred that the material have a surface area of atleast 20 m. g. In carrying out the reduction hereunder any suitablereducing atmosphere can be used including hydrogen, carbon monoxide,mixtures of hydrogen and carbon monoxide, mixtures of these with diluentgases, etc.

It is to be understood that the above disclosure is by way of specificexample and that numerous modifications and variations in the alloymaterials and methods for their preparation and utilization areavailable to those of ordinary skill in the art without departing fromthe true spirit and scope of our invention.

We claim:

1. A catalyst consisting of metallic nickel, a second metallic componentselected from the class consisting of molybdenum, tungsten and mixturesthereof, the mol ratio of nickel to said second component being betweenabout 50 to l and about 0.2 to 1, and less than 25 percent of an oxideor oxides of said metals, said nickel and said second componentassociated together as -an alloy, and said catalyst having a surfacearea of at least about one square meter per gram.

2. A catalyst in accordance with claim 1 on a solid catalyst support.

3. A catalyst in accordance with claim 2 in which the second componentis tungsten.

4. A catalyst in accordance with claim 2 in which the second componentis molybdenum.

5. A catalyst in accordance with claim 2 in which the mol ratio ofnickel to said second component is from about 15 to one to about one toone.

6. A composition in accordance with claim 2 in which the surface area isat least about 20 m. g.

7. A catalyst in accordance with claim 1 in which the mol ratio ofnickel to said second component is from about 15 to one to about one toone.

8. A method for producing the catalyst of claim 1 which comprisesheating a mixture of reducible compounds of said metals in a reducingatmosphere at a first temperature between about 100 and 250 C. andfurther heating the partially reduced mixture in a reducing atmosphereat a second temperature above about 250 C. and up to about 600 C.

9. A method for producing the catalyst of claim 2 Which comprisesheating a mixture of reducible compounds of said metals in the presenceof said solid catalyst support in a reducing atmosphere at a firsttemperature between about 100 and 250 C. and further heating thepartially reduced mixture in a reducing atmosphere at a secondtemperature above about 250 C. and up to about 600 C.

10. A method in accordance with claim 9 in which said reducingatmosphere contains hydrogen and said second temperature is betweenabout 300 and 500 C.

11. A method in accordance with claim 10 in which said second componentis molybdenum.

12. A method in accordance with claim 10 in which said second componentis tungsten.

13. A method of producing sulfided alloys of nickel and a secondcomponent selected from the group consisting of molybdenum, tungsten andmixtures thereof which comprises heating a mixture of reduciblecompounds of nickel and a second component selected from the groupconsisting of molybdenum, tungsten and mixtures thereof, the mol ratioof nickel to the second component as the metals being between about to 1and about 1 to .1, in a reducing atmosphere at a first temperaturebetween about 100 and about 250 C., further heatmg the partially reducedmixture in a reducing atmosphere at a second temperature above about 250and up to about 600 C., and finally heating the reduced product in asulfiding atmosphere at a temperature between about 250 C. and about 400C.

14. A method for producing sulfided alloys in accordance with claim 13in which the reducible compounds of nickel and the second component areon a solid catalyst support.

15. A method in accordance with claim 14 in which said second componentis molybdenum.

16. A method in accordance with claim 14 in which said second componentis tungsten.

17. The sulfided catalyst consisting of the sulfided alloy of nickel anda second component selected from the group consisting of molybdenum,tungsten and mixtures thereof as produced by the method of claim 13.

18. The supported sulfided catalyst consisting of the sulfided alloy ofnickel and a second component selected from the group consisting ofmolybdenum, tungsten and mixture thereof on a solid catalyst support asproduced by the method of claim 14.

References Cited UNITED STATES PATENTS 2,650,906 9/1953 Engel et a1.252-470 2,744,052 5/1956 Nozaki 25243'9 X 2,948,687 8/1960 Hadley 252470PATRICK P. GARVIN, Primary Examiner US. Cl. X.R.

252-470; l70; 208--l.l2; 26 0-68165

